Thermal Rearrangement of Osmabenzenes to Osmium Cyclopentadienyl Complexes
| Autor: | L. James Wright, Warren R. Roper, Scott D. Woodgate, Paul M. Johns |
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| Rok vydání: | 2010 |
| Předmět: | |
| Zdroj: | Organometallics. 29:5358-5365 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/om1003754 |
| Popis: | The purple osmabenzene complex Os(C5H4{SMe-1})(CF3SO3)(CO)(PPh3)2 (1) is formed in high yield through reaction between Os(C5H4{S-1})(CO)(PPh3)2 and methyl triflate. The neutral blue osmabenzenes Os(C5H4{SMe-1})(cis-X)(CO)(PPh3)2 (X = I (2a), Cl (2b), SCN (2c), CF3CO2 (2d)) are readily obtained through treatment of 1 with the appropriate anion X−. In these complexes the geometry about osmium is approximately octahedral, with the two PPh3 ligands being mutually trans and X being cis to the SMe-substituted carbon of the metallabenzene ring. When solutions of 2a in benzene are heated under reflux, the I and CO ligands interchange positions and the brown isomeric osmabenzene Os(C5H4{SMe-1})(trans-I)(CO)(PPh3)2 (3a) is formed. However, if a solution of either 2a or 3a is heated under reflux in toluene, the metal-bound carbon atoms of the osmabenzene fragment couple and a mixture of the two cyclopentadienyl complexes [Os(η5-C5H4SMe)(CO)(PPh3)2]I (4a) and Os(η5-C5H4SMe)I(CO)(PPh3) (5a) is formed. Heating solution... |
| Databáze: | OpenAIRE |
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